DE1138048B - Process for the preparation of (thiono)phosphonic or (thiono)phosphinic acid esters of ª‡- and ª‰-naphthols - Google Patents

Description

GERMAN

PATENT OFFICE

F 30217 IVb / 12 ο

REGISTRATION DATE: DECEMBER 31, 1959

NOTICE
THE REGISTRATION
AND ISSUE OF THE
EDITORIAL: OCTOBER 18, 1962

It has been found that in a manner known in principle to new (thiono) phosphonic or (Thiono) phosphinic acid esters of the general formula

OR ₃

R ₂

obtained by (thiono) phosphonic (yne) acid halides of the general formula

R ₁ . (XS)

P - shark

with a- or / J-naphthols, which may optionally be substituted in the nucleus by 1 chlorine or bromine atom, where Ri and R ₂ stand for alkyl, phenyl or chlorophenyl radicals, R ₂ can also be an alkoxy radical, R _{3 is} an α- or α-naphthyl radical, which may optionally be substituted in the nucleus by 1 chlorine or bromine atom, and Hal is a halogen atom.

It is sometimes convenient to add the reaction mixture to accelerate this esterification reaction add a small amount of catalytically active copper powder.

The compounds of the invention are potent pesticides that except an insecticidal effect surprisingly have an internal therapeutic fungicidal effect, which has not yet been observed in the group of organic phosphoric acid compounds.

This systemic fungicidal activity was found when the compounds according to the invention were tested by the so-called Dimond test on tomatoes for combating Fusarium oxysporum lycopersici. For example, the phenyl-thionophosphonic acid-O-ethyl-O- (β- naphthyl) ester which can be prepared by the process according to the invention acts systemically against Fusarium oxysporum lycopersici in an application rate of 0.012%. However, the phosphonic or phosphinic acid processes obtainable according to the process for the production of were also found when used against Fusarium cubense on bananas, Omphalia flavida on coffee, Verticillium alboatrum on the egg plant and Alternaria solani on cabbage

(Thiono) phosphonic resp.

(Thiono) phosphinic acid esters der

α- and ß-naphthols

Applicant:

Paint factories Bayer Aktiengesellschaft, Leverkusen

Dr. Dr. H. c. Gerhard Schrader,

Wuppertal-Cronenberg, and

Dr. Hanshelmut Schlör, Wuppertal-Barmen,

have been named as inventors

esters of α- and / J-naphthols as systemically effective Fungicides.

Furthermore, the above-mentioned phenyl-thionophosphonic acid-O-ethyl-O- (jS-naphthyl) ester obtainable according to the process has also when used against Fusicladium dendriticum on tomatoes in comparison to those from the literature as fungicidal effective known compounds of analogous composition have a superior effectiveness. 0.012% / qige Solutions of the compound according to the invention are still 100% pure against the harmful fungus mentioned systemically fungicidal. This means that the useful plants when using the product in the indicated application rate are no longer infested with Fusicladium dendriticum.

In contrast, the a- (O, O-diethylthionothiolphosphoric acid) known from US Pat. No. 2,644,002 - N - (4 - chlorophenyl) - succinimide and the Ο, Ο-diethylthionothiolphosphoric acid S- (j? - [N-methylcarbonylamino] ethyl) ester and the O, O-dimethylthionothiolphosphoric acid -S- (1,2-dicarbäthyloxyäthyl) ester known from British patent 794 597 when used in the same concentration, no systemic fungicidal effect whatsoever against the phytopathogenic mentioned Mushroom.

The following examples illustrate the process according to the invention:

209 677/341

example C ₂ H ₅ O 1 CH ₃ S P-O- /

42 g (0.25 mol) of S-naphthol sodium are dissolved in 200 ml of methyl ethyl ketone. Thereto is added with stirring at 30 to 40 ⁰ C. 40 g Methyl-thionophosphonsäure-O-äthylesterchlorid (Kp-I ₂ 6O ⁰ C). The reaction product is kept at 40 ° C. for 1 hour and then poured into 400 ml of ice water. The oil which has separated out is taken up in 300 ml of benzene and washed neutral with a 3% strength aqueous sodium bicarbonate solution. The benzene solution is dried with sodium sulfate and fractionated. 37 g of the new ester with a boiling point of 0.01 123 ° C. are obtained in this way. Yield 56% of theory. Rat per os mean toxicity 250 mg / kg.

Example 2

144 g (1 mol) of ^ -naphthol are dissolved in 1000 ml of benzene. Add 150 g of finely powdered, anhydrous potassium carbonate mixed with 1 g of copper powder. With good stirring is added dropwise at 8O ⁰ C 221 gPhenyl-thionophosphonsäure-0-äthylesterchlorid (Kp. _O, oi 75 ° C) added. It is kept at 80 ° C. for 3 hours, then cooled to room temperature and 100 ml of water are added. The salts formed are filtered off with suction and the filtrate is washed with a 3% strength sodium bicarbonate solution. The benzene solution is then dried with sodium sulfate. Then the benzene is evaporated in vacuo. In this way, 225 g of the new ester are obtained as a yellow-brown, water-insoluble liquid. Yield 690/0 of theory. Average toxicity rat orally 1000 mg / kg.

Example 5

C ₂ H ₅ O

42 g (0.25 mol) / 3-naphthol sodium are dissolved in 200 ml of methyl ethyl ketone. 36 g of methyl phosphonic acid O-ethyl ester chloride (boiling point ₂ 45 ° C.) are then added at 30.degree. The mixture is left for 1 hour at 3O ⁰ C stirring and then worked up as in Example. 1 In this way, 36 g of the new ester with a boiling point of 0.01 115 ° C. are obtained. Yield 58% of theory. Average oral toxicity in rats 250 mg / kg.

Example 3

45

42 g (0.25 mol) of ß-naphthol sodium are dissolved in 200 ml of methyl ketone. To the solution are added at 4O ⁰ C 33 g of dimethyl thionophosphinsäurechlorid. The mixture is heated to 40 ^° C. for a further hour, then the reaction product is added to 400 ml of ice water. The oil which has separated out is taken up in 300 ml of benzene. The benzene solution is washed neutral with a 3% strength aqueous sodium bicarbonate solution. The benzene solution is then dried with sodium sulfate. When the solvent is distilled off, the new ester solidifies in crystalline form. Recrystallized from ethyl acetate-ligroin, it has a melting point of 88 to 89 ° C. 45 g of the new ester are obtained in this way. Yield 76% of theory. Average toxicity rat orally 1000 mg / kg.

Example 6

C ₂ H ₅ O

42 g (0.25 mol) of sodium 9-naphthol are dissolved in 200 ml of methyl ethyl ketone. At 40 ⁰ C are added with stirring 44 g of ethyl-thionophosphonsäure-O-äthylesterchlorid (Kp ,! 48 ⁰ C) was added. It is kept at 40 ^° C. for 1 hour and then worked up as in Example 1. 64% of theory are obtained in this way 45 g of the new ester by Kp.o, oi 128 ⁰ C. yield. Average oral toxicity in rats 500 mg / kg.

60

Example 4

C ₂ H ₅ O

C ₂ H ₅ O

36 g (0.2 mol) of 1-chloro-2-naphthol (melting point 70 ° C.) are dissolved in 300 ml of benzene and a sodium methylate solution containing 0.2 mol of dissolved sodium is added with stirring. Then benzene and methanol are distilled off in vacuo. The remaining sodium salt is dissolved in 200 ml of methyl ethyl ketone. At 30 ° C., 44 g of phenylthionophosphonic acid O-ethyl ester chloride are then added dropwise with thorough stirring. The mixture is heated to 40 ^° C. for a further hour and then worked up in the usual way. In this way, 62 g of the new ester are obtained as a dark brown, water-insoluble oil. Yield _830/0 of theory.

. Cl

45 g (0.2 mol) of 1-bromo-2-naphthol (melting point 86 ^° C.) are dissolved in 300 ml of benzene. A sodium methylate solution containing 0.2 mol of sodium in dissolved form is added to the solution. Benzene and methanol are then distilled off in vacuo. The sodium salt obtained is dissolved in 200 ml of methyl ethyl ketone. Is then added with stirring 41 g of isopropyl-O-thionophosphonsäure äthylesterchlorid (Kp. ₂ 50 ⁰ C) at 40 ⁰ C added. It is kept at 40 ^° C. for a further hour and then worked up in the usual way. 58 g of the new ester are thus obtained as a dark brown, water-insoluble oil. Yield 78% of theory.

This gives 57 g of the new ester as a white crystalline mass. Recrystallized from ethyl acetate ligroin, the ester is obtained in colorless needles with a melting point of 118.degree. Yield 63% of theory.

Example 10

C ₂ H ₅ O

22 g (0.1-5 mol) / 9-naphthol are dissolved in 250 ml of benzene. A sodium methylate solution containing 0.15 mol of sodium in solution is added to the solution. Benzene and methanol are then distilled off in vacuo. The sodium salt obtained is dissolved in 250 ml of methyl ethyl ketone. Is then added with vigorous stirring at 40 ⁰ C 39 g of p-chlorophenyl - thionophosphonsäure - O - äthylesterchlorid (Kp-3 Γ 13 C) was added. Keeping for 1 hour at 4O ⁰ C and then worked up in the usual manner. In this way 44 g of the new ester are obtained as a dark brown, water-insoluble oil. Yield 61% of theory.

Example 8

(CHa) ₂ CH S

P-O

C ₂ H ₅ O

36 g (0.25 mol) ^ -naphthol are dissolved in 50 ml of methanol. A sodium methylate solution containing 0.25 mol of sodium in dissolved form is added. The mixture is stirred for a quarter of an hour at 60 ^° C. and then 30 ml of benzene are added. Benzene and methyl alcohol are then distilled off in vacuo. The remaining sodium salt is taken up in 200 ml of acetonitrile. Under stirring were then added at 40 ⁰ C, 64 g of diphenyl-thionophosphinsäurechlorid (Kp. _0, i 15O ⁰ C) was added. It is kept at 40 ^° C. for 1 hour and then worked up in the usual way.

36 g (0.25 mol) / ^ - naphthol are converted into the sodium salt in the usual way with the equivalent amount of sodium methylate. The sodium salt is dissolved in 200 ml of acetonitrile. To the solution are added at 4O ⁰ C 48 g methylphenyl thionophosphinsäurechlorid (Kp.j 90 ⁰ C). The mixture is heated for 1 hour at 4O ⁰ C and then worked up in the usual manner. 50 g of the new ester are thus obtained as a dark brown, water-insoluble oil. Yield 67% of theory.

Example 11

C ₂ H ₅ O

36 g (0.25 mol) of α-naphthol are dissolved in 300 ml of benzene. A sodium methylate solution containing 0.25 mol of sodium in solution is added. Benzene and methyl alcohol are then distilled off in vacuo. The sodium salt obtained is taken up in 200 ml of methyl ethyl ketone. At 40 ⁰ C is allowed to this solution dropwise 40 g Methylthionophosphonsäure-O-äthylesterchlorid.

The reaction product is kept for a further 1 hour

to 40 ⁰ C and then works on in the usual way.

42 g of the new ester with a boiling point of 119 ° C. are thus obtained. Yield 63 <V ₀ of theory. Average toxicity rat orally 100 mg / kg.

Example 12

C ₂ H ₅ O

Similarly, from 36 g (0.25 mol)

a-naphthol and 44 g of ethyl thionophosphonic acid

O-ethyl ester chloride 35 g of the new ester. The ester boils under a pressure of 0.01 mm at 120 ^° C.

Yield 50% of theory.

Example 13 Example 16

36 g (0.25 mol) of a-naphthol are converted into the sodium salt in the usual way. This is dissolved in 200 ml of methyl ethyl ketone. Then add-phosphonic acid-O-methyl äthylesterchlorid at 30 ⁰ C. 36 g. The mixture is kept at 30.degree. C. for 1 hour and then worked up in the customary manner. There are thus 42 g of the new ester by Kp. _O obtained oi 114 ° C. Yield 66% of theory.

45 g (0.2 mol) of 1-bromo-2-naphthol are converted into the sodium salt and this is dissolved in 300 ml of methyl ethyl ketone. At 2O ⁰ C allowed 44 g (0.2 mol) of _phenyl-S thionophosphonsäure-äthylesteri chloride added dropwise and holding for 1 hour at 60 ⁰ C. After the usual working up, 65 g of the new ester as a light brown oil. Yield 80% of theory.

Example 17 Example 14

P-O

C ₂ H ₅ O

36 g (0.25 mol) of a-naphthol are dissolved in 300 ml of benzene. A sodium methylate solution containing 0.25 mol of sodium in dissolved form is added. Is maintained for 1 hour at 6O ⁰ C and then distilled benzene and methyl alcohol in a vacuum. The sodium salt obtained is dissolved in 200 ml of methyl ethyl ketone. At 40 ⁰ C., then added 56 g of phenyl-thionophosphonsäure-O-äthylesterchlorid. It is kept at 40 ^° C. for a further hour and then worked up in the usual way. This gives 65 g of the new ester as a brown, water-insoluble oil. Yield 79% of theory. In rats per os, 1000 mg / kg did not yet show any symptoms.

Example 15

In a similar manner, 29 g (0.2 mol) of α-naphthol and 41 g (0.2 mol) of phenylthionophosphonic acid methyl ester chloride are obtained 54 g of the new ester. Yield 86% of theory.

Example 18

By reacting 36 g (0.2 mol) of 1-chloro-2-naphthol with 35 g (0.2 mol) of ethyl thionophosphonic acid ethyl ester chloride, 52 g of the are obtained the above ester. Yield 83% of theory.

Example 19

55

29 g (0.2 mol) ^ -naphthol are converted in the usual way into the sodium salt, which is dissolved in 300 ml of methyl ethyl ketone. Then allowed to 41 g (0.2 mol) of phenyl-thionophosphonsäuremethylesterchlorid (Kp. _X 98 to 99 ° C) is added dropwise, maintaining the temperature by cooling at 20 ⁰ C. Is then heated for 1 hour at 6O ⁰ C and worked up in the usual manner. 51 g of the new ester are obtained as a water-insoluble oil. Yield 81% of theory.

When 45 g (0.2 mol) of 1-bromo-2-naphthol are reacted with 32 g (0.2 mol) of diethyl thionophosphinic acid chloride, 58 g of the specified ester are obtained. The product has a melting point of 38 to 41 ^° C. and can be recrystallized from cyclohexane. Yield 85% of theory.

Example 20

C ₂ H ₅ OS

Mix equal parts of ethyl acetate-ligroin in colorless needles with a melting point of IH ⁰ C.

Example 24

From 45 g (0.2 mol) of 6-bromo-2-naphthol (melting point 125 to 127 ° C.) and 44 g (0.2 mol) of phenylthionophosphonic acid ethyl ester chloride 65 g of the specified compound are obtained. Yield 80% of theory.

Example 21

C ₂ H ₅ O

By reacting 45 g (0.2 mol) of 1-bromo-2-naphthol with 39 g (0.25 mol) of methyl thionophosphonic acid ethyl ester chloride, 51 g of the one shown is obtained Esters. Yield 74% of theory.

Example 22

35 72 g (0.5 mol) / S-naphthol are dissolved in 50 ml of methanol. A sodium methylate solution which contains 0.5 mol of sodium in solution is added to this. Then, as in the previous example, 300 ml of benzene are added and methyl alcohol and benzene are distilled off azeotropically. The remaining sodium salt of ^ -naphthol is dissolved in 200 ml of acetonitrile. 161 g of 4,4-dichlorophenyl-thionophosphinic acid chloride (melting point 86 to 87 ° C.) are added at 40 ° C. with stirring. After the usual work-up, 129 g of the new ester are obtained as a viscous, water-insoluble oil. Yield 61% of theory.

Calculated

for moles 429 ... Cl 16.6 <> / ₀ , P7.2 <> / ₀ , S7.5 <V ₀ ; found Cl 16.6%, P 7.40 / ₀ , S 7.8 <> / ₀ .

P-O

C ₂ H ₅ O

In the usual way, 45 g (0.2 mol) of 6-bromo-2-naphthol are used reacted with 49 g (0.28 mol) of ethyl thionophosphonic acid ethyl ester chloride. You get 64 g of the new ester as a yellow-brown oil. Yield 79% of theory.

Example 23 CH ₃ = / CH ₃ S P-O-

45

50

72 g (0.5 mol) of a-naphthol are dissolved in 50 ml of methanol. A sodium methylate solution which contains 0.5 mol of sodium in solution is added to this. 300 ml of benzene are then added and benzene and methyl alcohol are distilled off azeotropically. The remaining sodium salt of α-naphthol is dissolved in 200 ml of acetonitrile. At 45 ⁰ C is then added with stirring 65 g of dimethyl thionophosphinsäurechlorid added (Kp.i 46 ° C). The mixture is heated to 50 ^° C. for a further hour and then the reaction product is added to 400 ml of ice water. The separated oil is taken up with benzene and washed through with water. After the usual work-up, 70 g of the new ester are obtained. Yield 62% of theory. The ester crystallizes from a Ge-To a solution of 36 g (0.25 mol) ^ -naphthol in 100 ecm of methanol, a sodium methylate solution containing 0.25 mol of sodium is added. After adding 300 ecm of benzene, methanol and benzene are removed by azeotropic distillation and the remaining sodium salt of / 9-naphthol is taken up in 200 ecm of methyl ethyl ketone. The resulting solution is mixed under stirring at 30 ° C with 47 g (0.25 mol) of tert-butylphosphonic acid-O-äthylesterchlorid (Kp.i 54 ° C), the reaction mixture then heated for 2 hours at 6O ⁰ C and poured it then in 300 ecm ice water. The precipitated oil is taken up in 200 ecm benzene, the benzene solution is washed with water until it reacts neutral, dried over sodium sulfate and fractionally distilled. After evaporation of the solvent gives 40 g (55% of theory) of tert-butylphosphonic acid-O-ethyl-O- (j3-naphthyl) ester from Kp.0,01 119 ⁰ C.

The compound has a mean toxicity (DL ₅₀ ) of 1000 mg per kilogram of animal in the rat per os.

209 677/341

11 1 138 048 12th Example 26 Example 28 O OC ₂ H ₅
—Ρ ¹ / 5 S OC ₂ H ₅
II /
sec. C ₄ H ₉ - P

Under reaction conditions similar to those in Example 25, 44 g (60% of theory) of tert-butyl are obtained from 36 g (0.25 mol) of a-naphthol and 47 g (0.25 mol) of tert-butylphosphonic acid O-ethyl ester chloride phosphonic acid-O-ethyl-O- (a-naphthyl) ester from Kp.o obtained oi 120 ⁰ C.

The mean toxicity (DL ₅₀ ) of the compound in rats is 1000 mg per os per kilogram of animal.

Example 27

sec. C ₄ H ₉ -

S OC ₂ H ₅

I /

A solution of 36 g (0.25 mol) ^ -naphthol in 1000 ecm of methanol is mixed with a sodium methylate solution containing 0.25 mol of dissolved sodium, then 3000 ecm of benzene is added to the reaction mixture and then methanol and benzene are azeotropically distilled off. The remaining sodium salt of ^ -naphthol as residue is dissolved in 200 ecm of methyl ethyl ketone. To this solution is added dropwise with stirring at 40 ⁰ C 51 g (0.25 mol) of sec.-butyl-O-thionophosphonsäure äthylesterchlorid, the mixture was heated for 1 hour at 40 ⁰ C and then as in Example 26 operates they described , on. The yield is 45 g (59% of theory) of sec-butyl-thionophosphonic acid-O-ethyl-O-OS-naphthyl) ester, which is obtained in the form of a water-insoluble, yellow oil.

Analysis for a molecular weight of 308:
Calculated .... S 10.4 <> / ₀ , P 10.0%;
found .... S 9.9%, P 9.4%.

The preparation has an average toxicity of over 1000 mg per kilogram in the rat per os Animal.

In a manner analogous to that described in the previous example, 36 g (0.25 mol) α-naphthol and 51 g (0.25 mol) of sec-butyl-thionophosphonic acid-O-ethyl ester chloride 57 g (74% of theory) of sec-butyl-thionophosphonic acid O-ethyl-O- (a-naphthyl) ester as a water-insoluble, yellow oil.

Analysis for a molecular weight of 308:

Calculates S 10.4 <> / ₀ , P 10.0 <y ₀ ;

found .... S 10.2 <y ₀ , P 9.6 <y ₀ .

The mean toxicity of the compound ₍₅ DL O) is more than 1000 mg per kg of rat when administered orally.

Claims (2)

PATENT CLAIMS: 1. Process for the production of (Thiono) Phos- Phonic or (thiono) phosphinic acid esters of α- and / S-naphthols, characterized in that (thiono) phosphonic acid halides of the general formula R ₁ O (S) P - shark in which R ₁ and R _{2 are} alkyl, phenyl or chlorophenyl radicals, R ₂ can also be an alkoxy radical and Hal is a halogen atom, with α- or / S-naphthols, which are optionally replaced by 1 chlorine or Bromine atom can be substituted, are implemented. 2. The method according to claim 1, characterized in that the reaction is in the presence is carried out by copper powder. Documents considered: German Auslegeschrift No. 1 046 045; British Patent No. 794 597; U.S. Patents Nos. 2,552,574, 2,586,655, 615 037, 2 615 038, 2 615 039, 2 644 002, 2 644 437, 774 706, 2 808 823, 2 876 245; Journal für Allgemeine Chemie (Russian), 29 (91), pp. 3289 to 3291, reported in the Chemisches Zentralblatt, 1961, p. 10 517.